organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890

rac-1-(2-Amino­carbonyl-2-bromo­eth­yl)pyridinium bromide

aBAM Federal Institute for Materials Research and Testing, Department of Analytical Chemistry, Reference Materials, Richard-Willstätter-Strasse 11, D-12489 Berlin-Adlershof, Germany
*Correspondence e-mail: robert.koeppen@bam.de

(Received 25 April 2012; accepted 2 May 2012; online 12 May 2012)

In the crystal structure of the title compound, C8H10BrN2O+·Br, inter­molecular N—H⋯Br hydrogen bonds link the mol­ecules into infinite chains along [001]. The inclined angle between the pyridine ring plane and the plane defined by the acid amide group is 63.97 (4)°.

Related literature

The title compound is an inter­mediate in the synthesis of 3-triphenyl­phospho­nium­bromidopropionitrile and 1-tri­phen­yl­phospho­nium­bromido-2-pyridinium-bromidoethane, see: Khach­ikyan et al. (2009[Khachikyan, R. D., Tovmasyan, N. V. & Indzhikyan, M. G. (2009). Russ. J. Gen. Chem. 79, 759-761.]).

[Scheme 1]

Experimental

Crystal data
  • C8H10BrN2O+·Br

  • Mr = 310.00

  • Monoclinic, P 21 /c

  • a = 8.6024 (9) Å

  • b = 16.1200 (19) Å

  • c = 9.5092 (12) Å

  • β = 121.501 (8)°

  • V = 1124.3 (2) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 7.18 mm−1

  • T = 296 K

  • 0.14 × 0.11 × 0.05 mm

Data collection
  • Bruker SMART APEX CCD area-detector diffractometer

  • Absorption correction: multi-scan (SADABS; Bruker, 2001[Bruker (2001). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.85, Tmax = 0.96

  • 10331 measured reflections

  • 2252 independent reflections

  • 1442 reflections with I > 2σ(I)

  • Rint = 0.106

Refinement
  • R[F2 > 2σ(F2)] = 0.044

  • wR(F2) = 0.129

  • S = 1.00

  • 2252 reflections

  • 118 parameters

  • H-atom parameters constrained

  • Δρmax = 0.96 e Å−3

  • Δρmin = −0.56 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
N2—H2A⋯Br2i 0.86 2.62 3.406 (7) 154
N2—H2B⋯Br2ii 0.86 2.57 3.428 (6) 173
Symmetry codes: (i) x-1, y, z; (ii) [x-1, -y+{\script{1\over 2}}, z-{\script{1\over 2}}].

Data collection: SMART (Bruker, 2001[Bruker (2001). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2001[Bruker (2001). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008)[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.] and ORTEPIII (Burnett & Johnson, 1996[Burnett, M. N. & Johnson, C. K. (1996). ORTEPIII. Report ORNL-6895. Oak Ridge National Laboratory, Tennessee, USA.]); software used to prepare material for publication: SHELXTL.

Supporting information


Comment top

rac-1-(2-Aminocarbonyl-2-bromoethyl)pyridinium bromide is an intermediate in the synthesis of 3-triphenylphosphoniumbromidopropionitrile and 1-triphenylphosphoniumbromido-2-pyridinium-bromidoethane (Khachikyan et al., 2009). The compound crystallizes in the monoclinic space group P21/c. The molecular structure of the compound and the atom-labeling scheme are shown in Fig 1. The molecules are arranged in such a way that the pyridyl rings are stagged with respect to each other. However, the distance between the molecular planes (dcentroids=4.295 (4) Å) indicates only weak π-π interactions. Each molecule is connected to two adjacent bromine anions via intermolecular N—H···Br hydrogen bonds (see dashed orange bonds in Fig. 2). As a result infinite chains are formed along [001] direction.

Related literature top

The title compound is an intermediate in the synthesis of 3-triphenylphosphoniumbromidopropionitrile and 1-triphenylphosphoniumbromido-2-pyridinium-bromidoethane, see: Khachikyan et al. (2009).

Experimental top

In a 250 ml, one-necked, round-bottomed flask fitted with a reflux condenser and a magnetic stirrer a mixture of 1.85 g of rac-2,3-dibromopropionic acid amide (7.98 mmol) and 0.63 g of pyridine (7.98 mmol) was diluted in 100 ml of acetonitrile and refluxed for 25 h. After cooling the flask was capped with a rubber septum equipped with a needle outlet for slow evaporation and then left in the dark at room temperature for 3 days. The obtained colorless crystals were suitable for direct single-crystal X-ray crystallography.

Refinement top

All H-atoms were positioned geometrically and refined using a riding model with d(C—H) = 0.93 Å, Uiso=1.2Ueq (C) for aromatic 0.98 Å, Uiso = 1.2Ueq (C) for CH, 0.97 Å, Uiso = 1.2Ueq (C) for CH2, 0.96 Å, Uiso = 1.5Ueq (C) for CH3 atoms, and 0.82 Å, Uiso = 1.5Ueq (C) for the amino group.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. : ORTEP representation of the title compound with atomic labeling shown with 30% probability displacement ellipsoids.
[Figure 2] Fig. 2. : View of the unit cell of the title compound along [100] (left) and [010] (right) showing the hydrogen-bonded chains along the [001] direction. Hydrogen bonds are drawn as dashed orange lines.
rac-1-(2-Aminocarbonyl-2-bromoethyl)pyridinium bromide top
Crystal data top
C8H10BrN2O+·BrF(000) = 600
Mr = 310.00Dx = 1.831 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 42 reflections
a = 8.6024 (9) Åθ = 4–25°
b = 16.1200 (19) ŵ = 7.18 mm1
c = 9.5092 (12) ÅT = 296 K
β = 121.501 (8)°Block, colourless
V = 1124.3 (2) Å30.14 × 0.11 × 0.05 mm
Z = 4
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer
2252 independent reflections
Radiation source: fine-focus sealed tube1442 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.106
ω/2θ scansθmax = 26.3°, θmin = 2.5°
Absorption correction: multi-scan
(SADABS; Bruker, 2001)
h = 1010
Tmin = 0.85, Tmax = 0.96k = 1918
10331 measured reflectionsl = 1111
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.044Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.129H-atom parameters constrained
S = 1.00 w = 1/[σ2(Fo2) + (0.0659P)2]
where P = (Fo2 + 2Fc2)/3
2252 reflections(Δ/σ)max < 0.001
118 parametersΔρmax = 0.96 e Å3
0 restraintsΔρmin = 0.56 e Å3
Crystal data top
C8H10BrN2O+·BrV = 1124.3 (2) Å3
Mr = 310.00Z = 4
Monoclinic, P21/cMo Kα radiation
a = 8.6024 (9) ŵ = 7.18 mm1
b = 16.1200 (19) ÅT = 296 K
c = 9.5092 (12) Å0.14 × 0.11 × 0.05 mm
β = 121.501 (8)°
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer
2252 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2001)
1442 reflections with I > 2σ(I)
Tmin = 0.85, Tmax = 0.96Rint = 0.106
10331 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0440 restraints
wR(F2) = 0.129H-atom parameters constrained
S = 1.00Δρmax = 0.96 e Å3
2252 reflectionsΔρmin = 0.56 e Å3
118 parameters
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Br10.23648 (10)0.06295 (5)0.72065 (9)0.0538 (3)
O10.3105 (6)0.2759 (3)0.8640 (6)0.0652 (15)
N10.6197 (6)0.1137 (3)0.7616 (6)0.0384 (12)
N20.0498 (7)0.2553 (4)0.6168 (7)0.0661 (18)
H2A0.00840.29350.63350.079*
H2B0.00380.22740.52630.079*
C10.3180 (8)0.1706 (4)0.6882 (7)0.0357 (14)
H10.28130.17610.57220.043*
C20.2227 (9)0.2392 (4)0.7308 (8)0.0460 (16)
C30.5231 (8)0.1790 (4)0.7954 (7)0.0408 (15)
H3A0.55910.23290.77640.049*
H3B0.55900.17620.91040.049*
C40.6778 (10)0.0453 (4)0.8562 (8)0.0487 (17)
H40.65890.03980.94350.058*
C50.7646 (11)0.0161 (5)0.8247 (9)0.061 (2)
H50.80300.06390.88910.073*
C60.7945 (10)0.0071 (5)0.6982 (10)0.061 (2)
H60.85610.04820.67780.073*
C70.7336 (10)0.0633 (4)0.6000 (9)0.0541 (18)
H70.75160.06980.51230.065*
C80.6458 (8)0.1229 (4)0.6362 (8)0.0432 (15)
H80.60380.17070.57200.052*
Br20.79943 (9)0.35088 (4)0.75292 (7)0.0465 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.0548 (5)0.0502 (5)0.0573 (5)0.0118 (3)0.0299 (4)0.0013 (3)
O10.047 (3)0.087 (4)0.050 (3)0.002 (3)0.018 (3)0.035 (3)
N10.038 (3)0.039 (3)0.038 (3)0.002 (2)0.020 (3)0.003 (2)
N20.045 (4)0.079 (4)0.054 (4)0.019 (3)0.012 (3)0.027 (3)
C10.044 (4)0.038 (3)0.027 (3)0.001 (3)0.020 (3)0.001 (2)
C20.049 (5)0.050 (4)0.041 (4)0.002 (3)0.025 (4)0.005 (3)
C30.040 (4)0.040 (4)0.044 (3)0.001 (3)0.022 (3)0.003 (3)
C40.059 (5)0.046 (4)0.041 (4)0.008 (3)0.026 (4)0.006 (3)
C50.068 (5)0.051 (5)0.057 (4)0.018 (4)0.028 (4)0.010 (4)
C60.045 (4)0.064 (5)0.067 (5)0.010 (4)0.024 (4)0.016 (4)
C70.051 (5)0.064 (5)0.053 (4)0.001 (4)0.032 (4)0.001 (4)
C80.039 (4)0.047 (4)0.043 (4)0.000 (3)0.020 (3)0.004 (3)
Br20.0511 (5)0.0474 (4)0.0384 (4)0.0015 (3)0.0216 (3)0.0004 (3)
Geometric parameters (Å, º) top
Br1—C11.956 (6)C3—H3A0.9700
O1—C21.235 (7)C3—H3B0.9700
N1—C81.333 (7)C4—C51.364 (9)
N1—C41.343 (8)C4—H40.9300
N1—C31.477 (7)C5—C61.363 (10)
N2—C21.330 (8)C5—H50.9300
N2—H2A0.8599C6—C71.386 (10)
N2—H2B0.8601C6—H60.9300
C1—C31.513 (8)C7—C81.373 (9)
C1—C21.550 (9)C7—H70.9300
C1—H10.9800C8—H80.9300
C8—N1—C4120.9 (5)N1—C3—H3B109.1
C8—N1—C3119.4 (5)C1—C3—H3B109.1
C4—N1—C3119.7 (5)H3A—C3—H3B107.9
C2—N2—H2A120.0N1—C4—C5120.3 (6)
C2—N2—H2B120.0N1—C4—H4119.9
H2A—N2—H2B120.0C5—C4—H4119.9
C3—C1—C2110.5 (5)C4—C5—C6119.5 (7)
C3—C1—Br1111.2 (4)C4—C5—H5120.2
C2—C1—Br1108.0 (4)C6—C5—H5120.2
C3—C1—H1109.1C5—C6—C7120.2 (7)
C2—C1—H1109.1C5—C6—H6119.9
Br1—C1—H1109.1C7—C6—H6119.9
O1—C2—N2124.5 (6)C8—C7—C6117.9 (6)
O1—C2—C1119.0 (6)C8—C7—H7121.1
N2—C2—C1116.4 (5)C6—C7—H7121.1
N1—C3—C1112.3 (5)N1—C8—C7121.2 (6)
N1—C3—H3A109.1N1—C8—H8119.4
C1—C3—H3A109.1C7—C8—H8119.4
C3—C1—C2—O118.5 (8)C8—N1—C4—C50.2 (10)
Br1—C1—C2—O1103.3 (6)C3—N1—C4—C5178.9 (6)
C3—C1—C2—N2160.2 (6)N1—C4—C5—C61.1 (11)
Br1—C1—C2—N278.1 (6)C4—C5—C6—C71.5 (12)
C8—N1—C3—C183.1 (7)C5—C6—C7—C81.0 (11)
C4—N1—C3—C196.1 (7)C4—N1—C8—C70.3 (9)
C2—C1—C3—N1178.7 (5)C3—N1—C8—C7179.4 (6)
Br1—C1—C3—N158.8 (6)C6—C7—C8—N10.1 (10)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2A···Br2i0.862.623.406 (7)154
N2—H2B···Br2ii0.862.573.428 (6)173
Symmetry codes: (i) x1, y, z; (ii) x1, y+1/2, z1/2.

Experimental details

Crystal data
Chemical formulaC8H10BrN2O+·Br
Mr310.00
Crystal system, space groupMonoclinic, P21/c
Temperature (K)296
a, b, c (Å)8.6024 (9), 16.1200 (19), 9.5092 (12)
β (°) 121.501 (8)
V3)1124.3 (2)
Z4
Radiation typeMo Kα
µ (mm1)7.18
Crystal size (mm)0.14 × 0.11 × 0.05
Data collection
DiffractometerBruker SMART APEX CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2001)
Tmin, Tmax0.85, 0.96
No. of measured, independent and
observed [I > 2σ(I)] reflections
10331, 2252, 1442
Rint0.106
(sin θ/λ)max1)0.624
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.044, 0.129, 1.00
No. of reflections2252
No. of parameters118
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.96, 0.56

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and ORTEPIII (Burnett & Johnson, 1996), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2A···Br2i0.862.623.406 (7)154
N2—H2B···Br2ii0.862.573.428 (6)173
Symmetry codes: (i) x1, y, z; (ii) x1, y+1/2, z1/2.
 

References

First citationBruker (2001). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationBurnett, M. N. & Johnson, C. K. (1996). ORTEPIII. Report ORNL-6895. Oak Ridge National Laboratory, Tennessee, USA.  Google Scholar
First citationKhachikyan, R. D., Tovmasyan, N. V. & Indzhikyan, M. G. (2009). Russ. J. Gen. Chem. 79, 759–761.  Web of Science CrossRef CAS Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar

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ISSN: 2056-9890
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